Coordination polymer adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Sol phase and sol-gel transition in SnO2 colloidal suspensions

The effect of concentration on the structure of SnO2 colloids in aqueous suspension, on their spatial correlation and on the gelation process was studied by small angle x-ray scattering (SAXS). The shape of the experimental SAXS curves varies with suspension concentration. For diluted suspensions ([SnO2] less than or equal to 0.13 mol L-1), SAXS results indicate the presence of colloidal fractal aggregates with an internal correlation length xi congruent to 20 Angstrom, without any noticeable spatial correlation between them. This suggests that the aggregates are spatially arranged without any significant interaction like in ideal gas structures. For higher concentrations ([SnO2] = 0.16, 0.32, and 0.64 mol L-1), the colloidal aggregates are larger (xi = 24 Angstrom) and exhibit a certain degree of spatial correlation between them. The pair correlation function corresponding to the sol with the highest concentration (0.92 mol L-1) reveals a rather strong short range order between aggregates, characteristic of a fluid-like structure, with an average nearest-neighbor distance between aggregates d(1) = 125 Angstrom and an average second-neighbor distance d(2) = 283 Angstrom. The pair distribution function remains essentially invariant during the sol-gel transition, suggesting that gelation involves the formation of a few points of connection between the aggregates resulting in a gel network constituted by essentially linear chains of clusters..

Transfer of radon and parent nuclides U-238 and U-234 from soils of the Mendip Hills area, England, to the water phase

Laboratory time scale experiments were conducted on soils from the Mendip Hills area, England, with the purpose of evaluating the release of Rn-222 and their parent nuclides U-238 and U-234 to the water phase and to determine the influence of parameters that can affect the geochemical behaviour of these nuclides in natural systems. The specific surface area of the samples ranged from 43.8 to 52.5 cm(2) g(-1), where the particle size for all soil horizons is lognormally distributed, with modal values of the particle radius undersize ranging from 107 up to 203 mu m. The values for the released radon were between 26 and 194 pCi, which allowed to estimate emanation coefficients for these materials between 0.1 and 0.2, within the context of other values reported elsewhere. Soils derived from Carboniferous limestone and characterized by higher pH, exchangeable calcium, and the presence of U, but with a lower U-231/U-238 activity ratio, yielded the highest values for released Rn; however, this trend was not observed for dissolved U and its respective U-234/U-238 activity ratio, when considering the less aggressive etchant. Uranium is mobilized from rock matrix to A and B horizons in the analysed soil profiles, where its enrichment is about 10 times higher in soils derived from Carboniferous limestone. These data also permitted an evaluation of a theoretical model for the generation of Rn in soils and its transfer to water, in order to interpret the radioactivity due to this gas in groundwaters from the Mendip Hills district, England. (C) 1999 Elsevier B.V. B.V. All lights reserved.

The effect of alpha-tocopherol on the oxidative cleavage of beta-carotene

Two cleavage pathways of beta-carotene have been proposed, one by central cleavage and the other by random (excentric) cleavage. The central cleavage pathway involves the metabolism of beta-carotene at the central double bond (15, 15') to produce retinal by beta-carotene 15, 15'-dioxygenase (E.C.888990988). The random cleavage of beta-carotene produces beta-apo-carotenoids, but the mechanism is not clear. To understand the various mechanisms of beta-carotene cleavage, beta-carotene was incubated with the intestinal postmitochondrial fractions of 10-week-old male rats for 1 h and cleavage products of beta-carotene were analyzed using reverse-phase, high-performance liquid chromatography (HPLC). We also studied the effects of alpha-tocopherol and NAD(+)/NADH on beta-carotene cleavage. In addition to beta-carotene, we used retinal and beta-apo-14'-carotenoic acid as substrates in these incubations. Beta-apo-14'-carotenoic acid is the two-carbon longer homologue of retinoic acid. In the presence of alpha-tocopherol, beta-carotene was converted exclusively to retinal, whereas in the absence of alpha-tocopherol, both retinal and beta-apo-carotenoids were formed. Retinoic acid was produced from both retinal and beta-apo-14'-carotenoic acid incubations only in the presence of NAD(+). Our data suggest that in the presence of an antioxidant such as alpha-tocopherol, beta-carotene is converted exclusively to retinal by central cleavage. In the absence of an antioxidant, beta-carotene is cleaved randomly by enzyme-related radicals to produce beta-apo-carotenoids, and these beta-apo-carotenoids can be oxidized further to retinoic acid via retinal. (C) 2000 Elsevier B.V.

Oxidative dissolution of research-grade minerals by Thiobacillus ferrooxidans and Thiobacillus thiooxidans

Solution- and solid-phase changes associated with galena (PbS) and sphalerite (ZnS) oxidation by T. ferrooxidans and T. thiooxidans, were determined. In experiments with galena, anglesite (PbSO4) was detected as a solid-phase product in biotic and abiotic experiments. In T. ferrooxidans cultures supplemented with FeSO4, jarosite [MFe3 (SO4)(2) (OH)(6)] was also detected as a new solid phase product, whereas SO was not detected in the residues. In sphalerite experiments, minor amounts of SO accumulated in FeSO4-amended sphalerite media with or without T. ferrooxidans or T. thiooxidans. Jarosite was only detected in T. ferrooxidans culture with FeSO4. By comparison with T. thiooxidans, T. ferrooxidans was more efficient in the oxidation of galena and sphalerite.

Effect of spin-polarized subbands in the inhomogeneous hole gas providing the indirect exchange in GaMnAs bilayers

The magnetic order resulting from the indirect exchange in the metallic phase of a (Ga,Mn)As/GaAs double layer structure is studied via Monte Carlo simulation. The polarization of the hole gas is taken into account, establishing a self-consistency between the magnetic order and the electronic structure. The Curie-Weiss temperatures calculated for these low-dimensional systems are in the range of 50-80 K, and the dependence of the transition temperature with the GaAs separation layer is established. (C) 2003 Published by Elsevier B.V.

Theoretical studies on the stability of N-methylformamide in both liquid and gas phases

Ab initio (restricted Hartree-Fock and DFT) and molecular mechanics calculations at MM2 level were performed for N-methylformamide (NMF) molecule and for three dimers in order to investigate the relative stability of the cis and trans conformers. The ab initio calculations show that no intramolecular interaction is relevant for the stability of the conformers explored. The trans conformer is the most stable. The MM calculations revealed that a double H-bonded cyclic cis-cis dimer is the most stable among the studied dimers, followed by a 'linear' H-bonded trans-trans dimer. This 'linear' dimer, however, is prevalent in the liquid phase. (c) 2006 Elsevier B.V. All rights reserved.

Determination of organochlorine pesticides and polychlorinated biphenyls residues in municipal solid waste compost by gas chromatography with electron-capture detection

A simple and efficient method for the simultaneous gas chromatographic determination of ten organochlorine pesticides (alpha-HCH, beta-HCH, gamma-HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, endrin, and dieldrin) and six congeners of PCBs (PCB 28, 52, 118, 138, 153, and 180) in municipal solid waste compost is described. The procedure involves a solid-phase dispersion matrix using celite as dispersant sorbent, alumina as clean up sorbent and hexane-dichloromethane (7:3, v/v) mixture as eluting solvent. An additional purification step with copper was necessary to eliminate sulphur. Analysis of the sample was performed by GC-ECD. The method was validated with fortified samples at two concentration levels (0.025 and 0.05 mg kg(-1)). Average recovery ranged from 77 to 121% with relative standard deviation between 1 and 18%. The detection limits, which ranged from 0.003 to 0.01 mg kg-1, were lower than those established by the Baden-Wurttemberg directive (0.033 mg kg(-1)).

The induction of cytotoxicity, oxidative stress, and genotoxicity by root canal sealers in mammalian cells

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

TEGDMA-induced oxidative DNA damage and activation of ATM and MAP kinases

The development of strategies for the protection of oral tissues against the adverse effects of resin monomers is primarily based on the elucidation of underlying molecular mechanisms. The generation of reactive oxygen species beyond the capacity of a balanced redox regulation in cells is probably a cause of cell damage. This study was designed to investigate oxidative DNA damage, the activation of ATM, a reporter of DNA damage, and redox-sensitive signal transduction through mitogen-activated protein kinases (MAPKs) by the monomer triethylene glycol dimethacrylate (TEGDMA). TEGDMA concentrations as high as 3-5 mm decreased THP-1 cell viability after a 24 h and 48 h exposure, and levels of 8-oxoguanine (8-oxoG) increased about 3- to 5-fold. The cells were partially protected from toxicity in the presence of N-acetylcysteine (NAC). TEGDMA also induced a delay in the cell cycle. The number of THP-1 cells increased about 2-fold in G1 phase and 5-fold in G2 phase in cultures treated with 3-5 mm TEGDMA. ATM was activated in THP-1 cells by TEGDMA. Likewise, the amounts of phospho-p38 were increased about 3-fold by 3 mm TEGDMA compared to untreated controls after a 24 h and 48 h exposure period, and phospho-ERK1/2 was induced in a very similar way. The activation of both MAPKs was inhibited by NAC. Our findings suggest that the activation of various signal transduction pathways is related to oxidative stress caused by a resin monomer. Signaling through ATM indicates oxidative DNA damage and the activation of MAPK pathways indicates oxidative stress-induced regulation of cell survival and apoptosis. (C) 2008 Elsevier Ltd. All rights reserved.

Irradiance stress responses of gas exchange and antioxidant enzyme contents in pariparoba [Pothomorphe umbellata (L.) Miq.] plants

We evaluated the growth and development of the medicinal species Pothomorphe umbellata ( L.) Miq. under different shade levels ( full sun and 30, 50, and 70 % shade, marked as I(100), I(70), I(50), and I(30), respectively) and their effects on gas exchange and activities of antioxidant enzymes. Photosynthetically active radiation varied from 1 254 mu mol m(-2) s(-1) at I(100) to 285 mu mol m(-2) s(-1) at I(30). Stomatal conductance, net photosynthetic rate, and relative chlorophyll (Chl) content were maximal in I(70) plants. Plants grown under I(100) produced leaves with lower Chl content and signs of chlorosis and necrosis. These symptoms indicated Chl degradation induced by the generation of reactive oxygen species. Stress related antioxidant enzyme activities ( Mn-SOD, Fe-SOD, and Cu/Zn-SOD) were highest in I(100) plants, whereas catalase activity was the lowest. Hence P. umbellata is a shade species ( sciophyte), a feature that should be considered in reforestation programs or in field plantings for production of medicinal constituents.

Sol-gel synthesis of mesoporous CaCu3Ti4O12 thin films and their gas sensing response

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Oxidative dissolution of covellite by Thiobacillus ferrooxidans

Oxidation of research-grade covellite was investigated in respirometric and growth experiments with Thiobacillus ferrooxidans. Covellite was directly oxidized by T. ferrooxidans in respirometric experiments, but the pH of mineral salts medium increased to prohibitively high values because of high sulfide concentrations. In glycine-H 2SO 4 buffered medium the pH remained steady and the oxygen uptake activity of T. ferrooxidans was not inhibited. In cultures growing with covellite as the sole source of energy, the pH increased to about 4. Redox potential increased to 500-600 mV during bacterial oxidation of covellite in the presence and absence of additional Fe 2+, whereas it remained mostly at about 350 mV in abiotic control. Jarosite was a major solid-phase product in T. ferrooxidans cultures. The solubilization of copper from covellite in inoculated flasks was higher than that obtained in control flasks and was not enhanced in the presence of additional Fe 2+.The sample also contained bornite (Cu 5FeS 4) which released iron in solution under all experimental conditions. Accumulation of S 0 was apparent only in inoculated covellite samples. © 1997 Elsevier B.V. All rights reserved.

Oxidative dissolution of chalcopyrite by Thiobacillus ferrooxidans

The oxidative dissolution of research-grade chalcopyrite was characterized in respirometric and growth experiments with Thiobacillus ferrooxidans. In respirometric experiments with chalcopyrite, the pH of mineral salts medium increased to values that inhibited the oxygen uptake activity of T. ferrooxidans. In glycine-H 2SO 4 buffered medium the pH remained stable and oxygen uptake was not inhibited. In cultures growing with chalcopyrite as the sole source of energy, pH changes were only minor during the incubation. The redox potential values increased to about 600 mV during the bacterial oxidation of chalcopyrite in the presence and absence of additional Fe 2+, while they remained at about 350 mV in abiotic control flasks. Iron in chalcopyrite was solubilized and oxidized to Fe 3+ by T. ferrooxidans. In the abiotic controls, by comparison, less iron was solubilized and it remained as Fe 2+. Jarosite was a major solid- phase product in T. ferrooxidans cultures. The solub'flization of copper from chalcopyrite in inoculated flasks was enhanced in the presence of additional Fe 2+.Accumulation of S 0, reflecting partial oxidation of the S-entity of chalcopyrite, was apparent from the x-ray diffraction analysis of solid residues from the inoculated flasks as well the abiotic controls. © 1997 Elsevier B.V. All rights reserved.

Determination of disease biomarkers in Eucalyptus by comprehensive two-dimensional gas chromatography and multivariate data analysis

In this paper is reported the use of the chromatographic profiles of volatiles to determine disease markers in plants - in this case, leaves of Eucalyptus globulus contaminated by the necrotroph fungus Teratosphaeria nubilosa. The volatile fraction was isolated by headspace solid phase microextraction (HS-SPME) and analyzed by comprehensive two-dimensional gas chromatography-fast quadrupole mass spectrometry (GC. ×. GC-qMS). For the correlation between the metabolic profile described by the chromatograms and the presence of the infection, unfolded-partial least squares discriminant analysis (U-PLS-DA) with orthogonal signal correction (OSC) were employed. The proposed method was checked to be independent of factors such as the age of the harvested plants. The manipulation of the mathematical model obtained also resulted in graphic representations similar to real chromatograms, which allowed the tentative identification of more than 40 compounds potentially useful as disease biomarkers for this plant/pathogen pair. The proposed methodology can be considered as highly reliable, since the diagnosis is based on the whole chromatographic profile rather than in the detection of a single analyte. © 2013 Elsevier B.V..